1. Field of the Invention
This invention relates generally to direct oxidation fuel cells, and more particularly, to fuel cells that operate with delivery of high concentration fuel and passive water management.
2. Background Information
Fuel cells are devices in which an electrochemical reaction involving a fuel molecule is used to generate electricity. A variety of compounds may be suited for use as a fuel depending upon the specific nature of the cell. Organic compounds, such as methanol or natural gas, are attractive fuel choices due to the their high specific energy.
Fuel cell systems may be divided into “reformer-based” systems (i.e., those in which the fuel is processed in some fashion to extract hydrogen from the fuel before it is introduced into the fuel cell system) or “direct oxidation” systems in which the fuel is fed directly into the cell without the need for separate internal or external processing. Many currently developed fuel cells are reformer-based systems. However, because fuel processing is complex and generally requires components which occupy significant volume, reformer based systems are presently limited to comparatively large, high power applications.
Direct oxidation fuel cell systems may be better suited for a number of applications in smaller mobile devices (e.g., mobile phones, handheld and laptop computers), as well as in some larger scale applications. In direct oxidation fuel cells of interest here, a carbonaceous liquid fuel (typically methanol or an aqueous methanol solution) is introduced to the anode face of a membrane electrode assembly (MEA).
One example of a direct oxidation fuel cell system is a direct methanol fuel cell system, or DMFC system. In a DMFC system, methanol or a mixture comprised of methanol and water is used as fuel (the “fuel mixture”), and oxygen, preferably from ambient air, is used as the oxidizing agent. The fundamental reactions are the anodic oxidation of the fuel mixture into CO2, protons, and electrons; and the cathodic combination of protons, electrons and oxygen into water.
Typical DMFC systems include a fuel source, fluid and effluent management sub-systems, and air management sub-systems, in addition to the direct methanol fuel cell itself (“fuel cell”). The fuel cell typically consists of a housing, hardware for current collection and fuel and air distribution, and a membrane electrode assembly (“MEA”), which are all typically disposed within the housing.
The electricity generating reactions and the current collection in a direct oxidation fuel cell system take place within and on the MEA. In the fuel oxidation process at the anode, the products are protons, electrons and carbon dioxide. Protons (originating from fuel and water molecules involved in the anodic reaction) migrate through the catalyzed membrane electrolyte, which is impermeable to the electrons. The electrons travel through an external circuit, which includes the load, and are united with the protons and oxygen molecules in the cathodic reaction, thus providing electrical power from the fuel cell and water product at the cathode of the fuel cell.
A typical MEA includes a centrally disposed protonically-conductive, electronically non-conductive membrane (“PCM”, sometimes also referred to herein as “the catalyzed membrane”). One example of a commercially available PCM is Nafion® a registered trademark of E.I. Dupont de Nemours and Company, a cation exchange membrane based on polyperflourosulfonic acid, in a variety of thicknesses and equivalent weights. The PCM is typically coated on each face with an electrocatalyst such as platinum, or platinum/ruthenium mixtures or alloy particles. On either face of the catalyst coated PCM, the electrode assembly typically includes a diffusion layer. The diffusion layer on the anode side is employed to evenly distribute the liquid fuel mixture across the catalyzed anode face of the PCM, while allowing the gaseous product of the reaction, typically carbon dioxide, to move away from the anode face of the PCM. In the case of the cathode side, a wet-proofed diffusion layer is used to allow a sufficient supply of oxygen by minimizing or eliminating the build-up of liquid, typically water, on the cathode aspect of the PCM. Each of the anode and cathode diffusion layers also assists in the collection and conduction of electric current from the catalyzed PCM.
Direct oxidation fuel cell systems for portable electronic devices should be as small as possible at the power output required. The power output is governed by the rate of the reactions that occur at the anode and the cathode of the fuel cell. More specifically, the anode process in direct methanol fuel cells based on acidic electrolytes, including polyperflourosulfonic acid and similar polymer electrolytes, involves a reaction of one molecule of methanol with one molecule of water. In this process, the oxygen atom in the water molecule is electrochemically activated to complete the oxidation of methanol to a final CO2 product in a six-electron process, according to the following chemical equationCH3OH+H2O=CO2+6H++6 e−  (1)
Since water is a reactant in this anodic process at a molecular ratio of 1:1 (water:methanol), the supply of water, together with methanol, to the anode at an appropriate weight (or volume) ratio is critical for sustaining this process in the cell. In fact, it has been known that the water:methanol molecular ratio in the anode of the DMFC has to significantly exceed the stoichiometric, 1:1 ratio shown by process (1). This excess is required to guarantee complete, 6 electron anodic oxidation to CO2, rather than partial oxidation to either formic acid, or formaldehyde, 4 e− and 2 e− processes, respectively, described by equations (2) and (3) below:CH3OH+H2O=HCOOH+4H++4 e−  (2)CH3OH=H2CO+2H++2 e−  (3)
Equations (2) and (3) describe partial processes that are not desirable and which might occur if anode water content is not sufficient during a steady state operation of the cell. Particularly, as is indicated in process (3), involving the partial oxidation of methanol, water is not required for this anode process and thus, this process may dominate when the water level in the anode drops below a certain point. The consequence of process (3) domination, is an effective drop in methanol energy content by 66% compared with consumption of methanol by process (1), which would result in a lower cell electric energy output. In addition, it might lead to the generation of a hazardous anode product (formaldehyde).
Typically, it has been difficult to provide in a tightly volume-limited DMFC technology platform, the high ratio water/methanol mixture at the anode catalyst that ensures effective and exclusive anode process (1). The conventional approaches to this problem can be divided into two categories:
(A) active DMFC systems, utilizing reservoirs of neat methanol and based on liquid pumping, and
(B) passive systems requiring no pumping, utilizing reservoirs containing methanol/water mixtures.
Class A, “active” systems that include pumping, can maintain, in principle, appropriate water content in the anode, by dosing neat methanol from a fuel delivery cartridge into an anode fluid recirculation loop. The loop typically receives water collected at the cathode and pumped back into the recirculating anode liquid. In this way, an optimized water/methanol anode mix can be maintained in a system with neat methanol in the cartridge. The concentration within the anode can be controlled using a methanol concentration sensor. The advantage of this approach is that neat methanol (100% methanol) or a very high methanol concentration solution can be carried in the cartridge. Carrying a high concentration fuel source maximizes the energy content of the overall system. The disadvantage of Class A systems is that while neat methanol can be carried in the cartridge, the system suffers from excessive complexity due to the pumping and recirculation components which result in significant parasitic power losses and increase in system volume. Such power losses can be particularly severe, relative to fuel cell power output, in the case of small scale power sources.
The class B systems, which are passive in nature, have the advantage of system simplicity achieved by potentially eliminating pumping and recirculation by using a design that carries a mixture of water and methanol in the fuel source reservoir. This type of system can be substantially completely passive as long as the rate of water loss through the cathode is adjusted by means of materials and structures. These materials and structures operate to match the reservoir composition so as to ensure zero net rate of water loss (or water accumulation) in the cell. The problem with this approach is that it requires that the system carries a significant amount of water together with the methanol in the cartridge. Carrying a methanol/water mix in the reservoir or cartridge, of a composition well under 100% methanol, results in a significant penalty in energy density of the power pack.
A fuel cell system that adapts the best features of both the Class A and Class B, (without the disadvantages of these two known systems,) would be quite advantageous. However, the possibility of supply of highly concentrated methanol, including 100% methanol, directly from a reservoir into the anode compartment, has not been considered practical without, at the same time, supplying water as well into the anode compartment by either collecting it from the cathode and externally pumping it back or, alternatively, directly feeding water from a reservoir of water-diluted methanol. In other words, the combination “Passive DMFC System” and “Neat Methanol Supply to the Anode” has not been considered feasible, as this has been fully expected to result in significant loss of methanol flowing across the membrane (significant methanol “cross-over”) and/or in an anode process different than (1).
There remains a need therefore, for a passive DMFC system, i.e., a system not requiring pumping and recirculation loops, that allows the direct supply of neat (100%) methanol to the anode. There remains a further need for such a system that passively maintains a water profile within the fuel cell, i.e., that will establish such desirable profile without active collection and pumping of water from the cathode, while using methanol in the tank or cartridge that is more concentrated than a 1:1 methanol/water mixture. Such a system should also include the additional important feature of effective management of anodically-generated carbon dioxide.
It is thus an object of the present invention to provide a direct oxidation fuel cell system that is capable of carrying highly concentrated, including neat (100%) methanol as the fuel source, and delivering such fuel directly to the anode; it is a further object that the cell of the present invention uses passive water management and effective passive carbon dioxide removal techniques.